Polyhaloalkylpolythioalkyl phosphate esters



United States Patent 01 Ffice 3,534,126 Patented Oct. 13, 1970 3,534,126 POLYHALOALKYLPOLYTHIOALKYL PHOSPHATE ESTERS Joseph E Moore, Richmond, Califl, assignor to Chevron Research Company, San Francisco, Calif., a corporation of Delaware No Drawing. Original application Oct. 20, 1966, Ser. No. 588,009. Divided and this application Mar. 28, 1969, Ser. No. 834,186

Int. Cl. C07c 141/00, 153/07; C07f 9/08 US. Cl. 260-947 Claims ABSTRACT OF THE DISCLOSURE Esters and ethers of the formula ROXS R where R' represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogens of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of 1 to 4 carbon atoms and m is an integer varying from 2 to 3, and R is an organic radical which forms an ester or ether with the remainder of the molecule. Typical R groups are hydrocarbyl, phosphoro, carbonyl, oxycarbonyl, sulfate and sulfonate groups. These esters and ethers are useful as fungicides.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisional of copending US. application Ser. No. 588,009, filed Oct. 20, 1966, which is a continuation-in-part of US. application Ser. No. 414,876, filed Nov. 30, 1964 and now abandoned and which in turn is a divisional of US. Patent No. 3,203,966.

This invention relates to novel esters and ethers which contain a polyhalo (lower) alkylpolythioalkyl group and their use as fungicides.

The compounds of this invention may be represented by the general formula:

ROXS R where R represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogens of atomic number 17 to 35, at least one of said halogens being bonded to the al ha carbon atom, X is alkylene of 1 to 4 carbon atoms, m is an integer varying from 2 to 3, and R is an organic radical which combined with OXS R' forms an ether or ester. Halogens of atomic number 17 to 35 are chlorine and bromine. The alpha carbon atom of the polyhaloalkyl group is bonded to a sulfur of the polysulfide m) p- X is an alkylene group from 1 to 4 carbons, e.g., methylene, ethylene, trimethylene, tetramethylene, isopropylene, 1,3-butylene, etc. The RO group is bonded to a primary carbon, that is, the carbon bonded to oxygen -has two hydrogens. Preferred alkylene groups contain 2 to 3 carbons.

The esters and ethers of this invention may be considered to be derivatives of alcohols. Thus, in a broad sense R is an organic radical which forms a bond with oxygen and may be cleaved on hydrolysis to regenerate the alcohol as follows:

uoxs s rnoa ROH+HOXS R' The R groups do not contribute significantly to the biological activity of the compounds of this invention. However, they may provide a means for special application or more attractive physical properties, e.g. hydrophobic, liphophilic, etc.

The R groups which form esters or ethers with OXS R contain 1 to about 12 carbon atoms. Included among such groups are aliphatic and aromatic hydrocarbyl groups such as alkyl, alkenyl and phenyl, carbacyl, alkoxycarbonyl, sulfate, sulfonate, borate and the like.

Among preferred R groups are the following:

where R is a halohydrocarbyl group having 0 to 1 halogens of atom number 17 to 35 and l to about 8 carbon atoms or a halohydrocarbylamino group having 0 to 1 halogens of atomic number 17 to 35 and 1 to about 8 carbon atoms,

GYR

where Y is a chalcogen atom of atomic number 8 to 16, i.e. O and S, R is a halohydrocarbyl group having 0 to 1 halogen of atomic number 17 to 35 and 1 to about 8 carbon atoms of halophenylthioalkyl in which the halo gen is of atomic number 17 to 35,

where R- is a hydrocarbyl group of 1 toabout 6 carbon atoms,

where R is OXS R as defined above,

0 H S Rs where R is OXS R' as defined above or alkyl, or

(f) Alkyl of 1 to about 6 carbon atoms.

Examples of radicals which R may represent are alkyl such as methyl, ethyl, hexyl and octyl, butenyl, phenyl, benzyl, tolyl; haloalkyl such as chloromethyl, chloroethyl, bromopropyl and chloroamyl, chloropropenyl, bromophenyl, chlorobenzyl, 4-chloro-6-methylpheny1; alkylamino such as methylamino, ethylamino, butylamino, hcxylamino and chlorobutylamino, chlorophenylamino, bromophenylamino, 6-bromo-2-methyl-phenylamino and the like.

Examples of specific groups which R may be are methyl, ethyl, isopropyl, hexyl, octyl, chloroethyl, chloropropyl, bromoamyl, chlorophenyl, bromobenzyl, chlorobutenyl, 6-chloro-2-methylphenyl, chlorophenylthio- 3 ethyl, bromophenylthiopropyl, chlorophenylthiobutyl and the like.

Examples of R are methyl, ethyl, propyl, hexyl, propargyl, butenyl and phenyl.

Illustrative of the novel compounds of this invention are the following compounds: fi-(trichloromethyldithio) ethyl benzoate; B-(perchloroethyldithio)ethyl acetate; fl-(l,1,2-trichloroethyldithio)ethyl benzoate; fi-(1,l,2,2- tetrachloroethyldithio)ethyl N ethylcarbamate; 13- (l,2,2,2 tetrachloroethyldithio) ethyl butyrate; di--y- (1,1,Z-trichloroethyldithio)-propyl carbonate; 'y-(1,1,2,2 tetrachloroethyldithio)-propyl S-ethyl thiolcarbonate; 'y- (perchloroethyltrithio)-propyl hexanoate, di-[fi-(1,2,2- trichloroethyldithio)ethyl] sulfate; di- [;6-( l,2,2,2-tetrachloroethyldithio)ethyl] sulfate; ethyl ,6-(1,1,2-trichlroethyldithio)ethyl sulfate; butyl 'y-(1-chloro-2,2-dibromoethyl)dithio propyl sulfate, di[,8-(trichloromethyldithio) ethyl] sulfite; di['y-(1,l,2,2-tetrachloroethyldithio)propyl] sulfitc; 0,0-dimethyl O-[ 3-(perchloroethyldithio) ethyl] phosphate; 0,0-dipropyl O-[fl-(1,2,2-trichloroethyldithio)ethyl] phosphate; 0,0-di phenyl O [B- (1,1,2,2-tetrachloroethyldithio)ethyl] phosphate; 0,0- dimethyl O-[;8-(perchloroethyldithio)propyl] phosphate, methyl-B-(trichloromethyldithio) ethyl ether, ethyl-' (1,1,2,2 tetrachloroethyltrithio)propyl ether, amyl-y- (perchloroethyldithio)propyl ether, and hexyl-fl-(tribromomethyldithio propyl ether.

Applicants novel compounds may be prepared according to general methods known in the art. The esters may be prepared by condensing an appropriate w-polyhaloalkylpolythio alkanol with an appropriate acid. Acidic compounds such as acids, acid anhydrides, and acid halides may be used according to procedures known in the art. When desirable, transesterification may also be used. Etherification may be achieved with sulfate esters, active halogen compounds and the alkoxide of the w-polyhaloalkylpolythio alcohol by methods known in the art. For making some of the compounds it may be preferable to prepare the oxygen derivative first and then contact the resulting mercaptan with the desired polyhaloalkylthio or thiosulfenyl halide.

The alcohol precursors of the compounds of this invention may be prepared by reacting a mercapto alcohol with a polyhaloalkylsulfenyl or -thiosulfenyl halide. Temperatures in the range of 0 to 50 C. may be used, but ambient temperatures or somewhat lower are preferred, that is, temperatures in the range of O to C. Various solvents may be used in the reaction which are inert to the reactants and products. Preferred solvents are halogenated hydrocarbons.

The following examples are offered as illustrative of the methods of preparation of the novel compounds of this invention:

Example I Into a flask fitted with condenser, thermometer, stirrer, and dropping funnel was introduced 8.5 grams of 1,1, 2,2-tetrachloroethylsulfenyl chloride in 100 ml. carbon tetrachloride. Into the mixture cooled in an ice bath was added 3.3 grams of a 61% solution of Z-methoxyethyl mercaptan diluted with carbon tetrachloride. The mercaptan was added dropwise and very slowly. After addition was completed, the reaction mixture was refluxed for about 10 minutes. The mixture was then allowed to cool to room temperature and the solvent stripped under a water vacuum. The residue was distilled yielding 4 grams of methyl-B41,1,2,2-tetrachloroethyldithio)ethyl ether boiling in a range of 100 to 117 C. at 0.4 to 0.6 mm. mercury.

Analysis.Theory (percent): Cl, 48.8; (percent): Cl, 46.4; S, 23.7.

The following table, Table I, lists other compounds of this invention which were prepared according to general procedures known in the art.

S, 22.1. Found TABLE 1 01 s NorP M.P., Structure C. Cale. Fd. Cale. Fd. Cale. Fd

it oera-s-s -c11,crn0c--c11a 30.4 34.3

i osi -s-s-s-0H1cH4-o-cNHcH3 4.4 3.8

0 ll (N) CHO1;CHClSSCHzCH0OCNH c1 35.0 30.2 35

1| oncn-cnci-s-s-crn-cm-o-r 0c1111): 28.1 25.0 11.0 10.0

l cci -oncl-s-s-cH,-c11,-cc0-OH20Hzsc1 00.2 36.8 107 10.0

ll oc1, c11o1-s-s-cH,oH1-0-o-s-o.r15 ass 41.0 20.4 25.5

u CCl;-CHC1-S-SCH4-OH;OG-NHC1 58-63 34 41 i1 co1, cnc1--s-s-cH2orn-o-c-NHcHa 42.5 40.3 10.3 10.0

ll CC1 CHC1SSCHqCH;O-P(00 E914 34.4 35.0 15.5 17.1 03

0 ll C(31 -011C1SS-CH1-CH O-CNH 58-60 05.0 35.0 10.2 10.0

TABLE 'I-Contin'ued O1 NorP Structure 63 Gale. F0. 0410. Fd. Cale. Fd;

oo1.-oHo1 s-s-oH, oH, o-ii-o1no1 50.3 40.0 13.2 20.2

onon-ccn-s-s-onz-oug-o-d-ou 44.3 43.3 20.1 20.5

oHo1,ocn-s-s-oH4oH5-oii-o-oH,-oH.-sQ01 33.2 35.0 10.7 20.0

oHon-oon-s-s-oH4-0H4o-h-o-orn-oH,-s@431 35.2 35.0 10.7 20.0

CHCh-CCl -SSCH CHg-O-iiI-SOl 30.0 34.0 21.5 23.3

oHon-oon-s-s-oH,-on,o h-s-on1 33.3 43.2 22.4 23.4

ouch-oon-s-s-oH,-oH.-oiiNH-c1 41.3 30.2 14.0 15.0 33 31 CHCl' CCl -SSCH=CHOii-NH 41.3 30.1 14.0 15.1

orron-oon-s-s-om-om-o-ii-mtom 42.5 40.1 10.3 10.0

[CHCl -CCl -S-S-CH -CH -OhS 40.2 50.0 25.1 25.0

[CHClg-CClz-SSCHz-CHz-O]S O 47.5 45.3 25.3 20.7

CHClr-CClr-S-S-CHz-CH:O(OC2H5)2 m 5.7

CHClr-CCIzS-S-CHzCHa-O%OCzHs- 36.8 40.7 25.0 25.4

CHCl -C Clr-SSCH4CH0OCH The novel compounds of this invention were tested for fungicidal activity against Pythium ultimum and Rhizoctonia solani by means of the mycelial drop test. This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhibition upon mycelial growth.

Each fungitoxic compound to be tested was dissolved in acetone in dilutions as indicated inthe following table. Paper discs previously inoculated by impregnation with equal amounts of a particular fungus mycelium and placed on potato dextrose agar medium were treated by applying a precise and equal volume of each of these fungicidal solutions to their center. Following treatment with the fungitoxic chemical, the discs were incubated along with inoculated but untreated control discs at ambient temperatures until such time as these untreated control discs were filled with mycelial growth. Activity of the fungitoxic chemical tested was determined by comparative measurements of radii of mycelial growth away from the edge of the disc in treated and untreated samples. From this comparison a percentage inhibition of growth area can be determined. The results are tabulated in columns I and II of Table II.

The novel compounds of this invention were also compared for fungicidal activity by means of The Standard Spore Slide-Germination Method for Determining Fungicidal Activity. The results obtained are expressed in terms of percent inhibition of germination of fungus spores.

Each compound to be tested was dissolved in acetone in dilutions to the desired concentration. These solutions were then pipetted into the wells of depression slides and allowed to dry. The wells were filled with a spore suspension of the test organism, Monilinia fructicola, and incubated in a moist chamber overnight. A group of onehundred spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percentage germination inhibition.

The results of these tests for various chemicals of this invention on the particular fungus mycelium and spores are indicated. as shown in column III of Table II.

TABLE II I II III Pythimn Rhizoctonia Monilinia Structure P.p.m. Percent P.p.m. Percent P.p.m. Percent 01 C1 6 (I: II 500 100 500 100 10 100 11- S-S-CH CH OC-OH 250 100 250 100 3 100 A} 125 100 150 72 1 100 C1 C1 0 I: (B H I 500 100 500 10 100 H- S--SCH CH OCO-CH OH S- Cl 250 80 3 62 C1 01 I l I s 0 ,cH 0 c-s- C1 1,000 29 1,000 9 1% 100 56 431 01 Cl Cl 0 I (I) II 1,000 100 1,000 100 10 100 H G -SS-CH CH2OCSCIIg-CH3 0 100 500 S8 3 100 6 (I3 250 100 250 40 C1 C1 0 A) II 500 100 500 100 10 100 H- S--SCH CH OCNH -01 250 100 250 33 3 100 I: I 125 11 l 48 Cl 01 01 o I (II; I 10 100 11* c-s s-0HzoH2o NE[ -l 3 94 01 C1 O (I: I II 500 100 500 100 10 100 H- C--S-SCH CH OC-NHCH 250 100 250 100 3 100 I I 125 100 125 86 1 100 C1 C1 01 G1 0 a I} II 500 100 500 94 10 100 H -SSCH GH O -S 250 100 250 38 3 100 I II 125 100 125 22 c. Cl 1 2 0 Cl 01 0 I) (I; II 1 10 100 H- -SS-CH OH O -S 3 67 1 30 l 1 Cl 01 O nOCz s (g (E 500 100 500 80 10 100 H- SS-CH CH;OP 250 79 250 3 100 01 01 II) IE[JI( JS -S --CL[ GH;O-S OO H 1, 000 100 1, 000 100 10 100 C1 01 I: (I; 1, 000 100 1,000 1,000 10 100 H- S-SCHg0HzO-CH3 500 100 500 78 250 15 l 1 Aside from the specific formulation and application of the class of compounds of the invention as represented by the foregoing test, these compounds may be dispersed in or upon other inert liquid and solid carriers such as inert clay, xylenes, etc. The solid carriers may be in the form of a dust, or used in conjunction .with a suitable wetting agent to form a wettable powder. The fungitoxic compounds of this invention may also be formulated with other solvents, dispersing agents, or emulsifying agents. Further, these compounds may not only be applied alone or in mixes with other compounds of the disclosed class, but may also be used in combination with other active toxicants in the formulation of fungicidal compositions.

The compounds may be applied to any environmental attack. For example, the fungicidal compositions may be sprayed or otherwise applied directly to a plant or other host, may be applied to the plant seed, sprayed upon the soil or other plant environment, or used in similar ways so as to effect the control of fungus and fungus caused diseases.

Obviously, many modifications and variations of the invention, as hereinabove set forth, may be made without departing from the spirit and scope thereof, and, therefore, only such limitations should be imposed as are indicated in the appended claims.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disarea which is a host to fungus or susceptible to fungus closure or from the scope of the following claims.

9 10 I claim: 5. Compounds of claim 1 wherein m is 2, R' is 1,1,2,2- 1. Compounds having the formula tetrachloroethyl or 1,1,2,2-tetrachloroethy1 and R is ethyl.

ll O X S References Cited where R represents a polyhaloalkyl group having 1 to 2 5 UNITED STATES PATENTS carbon atoms and 3 to 5 halogen atoms of atomic num- 2,724,718 11/ 1955 Stilfis et a 2609 7 X ber 17 to 35, at least one of said halogens being bonded to the alpha carbon atoms, X is alkylene of 1 to 4 car- CHARLES PARKER, Pnmary Exammer bon atoms, m is an integer varying from 2 to 3 and R m R, L RAYMON Assistant Examiner is a hydrocarbyl group of 1 to about 6 carbon atoms.

2. The compounds of claim 1 where m is 2. U.S. Cl. X.R.

3. The compounds of claimlwhere R is 1,1,2,2-tetra- 456 458 462 463 471 476 482 487 488 chloroethyl.

4. The compounds of claim 1 wherein R is alkyl, 15 424 215 336 

